US5171350A - Biocide - Google Patents
Biocide Download PDFInfo
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- US5171350A US5171350A US07/673,851 US67385191A US5171350A US 5171350 A US5171350 A US 5171350A US 67385191 A US67385191 A US 67385191A US 5171350 A US5171350 A US 5171350A
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- water
- biocide
- copper
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- 230000003115 biocidal effect Effects 0.000 title claims abstract description 28
- 239000003139 biocide Substances 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 30
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- 125000002091 cationic group Chemical group 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 244000005700 microbiome Species 0.000 claims description 7
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 241000589517 Pseudomonas aeruginosa Species 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims 2
- 230000002708 enhancing effect Effects 0.000 claims 1
- -1 transition metal cations Chemical class 0.000 abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 238000010790 dilution Methods 0.000 description 21
- 239000012895 dilution Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 12
- 238000009472 formulation Methods 0.000 description 10
- 230000012010 growth Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- DBHODFSFBXJZNY-UHFFFAOYSA-N 2,4-dichlorobenzyl alcohol Chemical compound OCC1=CC=C(Cl)C=C1Cl DBHODFSFBXJZNY-UHFFFAOYSA-N 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 6
- 229960004698 dichlorobenzyl alcohol Drugs 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 239000008233 hard water Substances 0.000 description 5
- 101100288310 Arabidopsis thaliana KTI2 gene Proteins 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000002906 microbiologic effect Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006150 trypticase soy agar Substances 0.000 description 4
- XVBRCOKDZVQYAY-UHFFFAOYSA-N bronidox Chemical compound [O-][N+](=O)C1(Br)COCOC1 XVBRCOKDZVQYAY-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000005791 algae growth Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000036512 infertility Effects 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000009182 swimming Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229940046305 5-bromo-5-nitro-1,3-dioxane Drugs 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical class [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000371004 Graesiella emersonii Species 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002353 algacidal effect Effects 0.000 description 1
- 230000002581 algistatic effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960003168 bronopol Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001332 colony forming effect Effects 0.000 description 1
- 238000012505 colouration Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000000937 inactivator Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229960005076 sodium hypochlorite Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008347 soybean phospholipid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
Definitions
- This invention relates to biocidal compositions for the treatment of water, and to methods for preventing microbial growth in water.
- oxidative substances such as hydrogen peroxide, sodium hypo-chlorite, and quaternary ammonium compounds such as n-alkyl dimethylbenzylammonium chlorides and n-alkyl dimethyl ethylbenzylammonium chlorides and analogous compounds.
- quaternary ammonium compounds such as n-alkyl dimethylbenzylammonium chlorides and n-alkyl dimethyl ethylbenzylammonium chlorides and analogous compounds.
- These substances are used to prevent microbial growth: that is to say they are added to water which has already been cleaned and sterilized (e.g. by filtration and chlorination), in order to maintain sterility. They are effective, typically at levels in the water of 10-100 ppm, although they do not necessarily provide a particularly wide spectrum of antimicrobial activity.
- transition metal cations especially copper II cations
- a cationic polyquaternary ammonium biocidal compound or a quaternary ammonium biocide comprising one long chain alkyl group and three other groups selected from lower alkyl and aralkyl groups, has advantageous properties.
- the combination of the quaternary compound and the metal ions in a concentrated aqueous system provides a stabilized metal ion solution which does not precipitate on dilution in the water to be treated. It may be theorized that the combination comprises some form of complex, since characteristic colour changes occur, e.g. the formation of an intense deep blue colour in dilute aqueous solutions of the copper II complex. The result is a distinct stabilization of the metal ions.
- the quaternary compounds of choice are poly[hydroxyethylene(dimethylimino) ⁇ '-hydroxypropyl dimethylimino)methylene-dichloride], hereinafter referred to as PHE, such as the product sold by ABM Chemicals Limited of Woodley. Stockport, Cheshire SK6 1PQ ; poly[2-hydroxyethylene(dimethylimino)ethylene(dimethylimino) methylene dichloride]; and poly[hydroxyethylene(dimerhylimino)ethylene(dimethylimino)ethylene dichloride].
- Other polymeric quaternary compounds comprise those carrying quaternised nitrogen atoms on side chains. Polyquaternary compounds are much preferred, giving good solubility and long lasting stability on dilution.
- Quaternary compounds such as didecyldimethyl ammonium chloride are unsatisfactory and tend to form insoluble complexes.
- Single quaternary compounds can be used, however, if the nitrogen atom is substituted by only one long chain alkyl group (e.g. C 12 -C 18 ), the remaining three substituents being lower alkyl, e.g. methyl, groups or aralkyl groups, e.g. benzyl or ethylbenzyl groups.
- the transition metal ion content in the mixture should be sufficient to give a level of about 0.5 to 3 ppm in the treated water when the quaternary compound is present in the water at about 30 to 50 ppm.
- the metal is advantageously copper, but may for example be zinc, chromium or tin.
- the concentrated mixture for addition to water can contain up to 50 or 60% of the quaternary compound and an equivalent amount of copper or other transition metal ions.
- biocidal composition containing a polymeric quaternary biocide, together with transition metal cations, especially copper II cations, and also a method of controlling microorganisms in water using such a composition.
- the quaternary biocides can also be enhanced in their bactericidal activity by formulation with a biocide of the type comprising a carbon atom substituted by a halogen atom and a nitro group, e.g. cyclic ##STR1## compounds and also 2-bromo-2-nitropropane-1,3-diol, supplied under the brand names Myacide by Boots Pure Drug Co., Nottingham and Bronopol by Henkel & Cie and 5-bromo-5-nitro-1,3-dioxane supplied under the brand name Bronidox by Henkel & Cie.
- Myacide is usually used at a level of about 50-100 ppm.
- Myacide or the like is formulated with a quaternary such as Glokill PQ so that at a dilution in water of the quaternary of about 20-30 ppm, the Myacide etc is present at about 0.5 to 5 ppm, the formulation is active against pseudomonads as well, even though the Myacide is present at levels far below those normally considered necessary.
- the two substances are mutually compatible, forming a stable co-solution concentrate and provide a powerful biocidal action on all water environments, especially pools and cooling towers.
- biocidal compositions containing a halonitro biocide, and a quaternary biocide a ratio of from 1:50 to 1:10 by weight, and also a method of controlling microorganisms in water, using such a composition.
- Sample 2 As Sample 1, but omitting the BNP
- Sample 4 As Sample 1, but replacing the BNP by 5-bromo-5-nitro-1,3-dioxan.
- TSA Tryptone Soya Agar
- SDW sterile distilled water
- a range of dilutions of the test solutions were prepared in sterile standard World Health Organization (WHO) Hard Water (see Appendix 1). At zero time P. aeruginosa inoculum was added to each dilution of each test solution to give approx. 10 6 organisms per ml. A control of sterile standard WHO hard water was also included. The tests were stored at 22° C. and sampled at 0 hours (control only), 24 hours, 48 hours and 72 hours. The number of viable bacteria was estimated using a pour plate technique (0.1% peptone water as diluent and TSA as growth medium). The pour plates were incubated at 30° C. for 3 days, surviving colonies counted and the dilution giving a 99.99% reduction in the bacterial population for each contact time calculated. The test was carried out on two separate occasions.
- WHO World Health Organization
- the PHE/BNP/Cu blend is a very effective bactericidal agent.
- WSCP and PHE are readily interchangeable so far as the bactericidal performance is concerned.
- Each formulation was made up in standard tap water (STW) and 20 ml. amounts of each were challenged with about 10 6 /ml P. aeruginosa NCTC 6750. Total viable counts (TVC's) were carried out in B.P. diluent and plated onto TSA at 0, 1, 2, 4 and 24 hours. Tests were stored at room temperature.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Zoology (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A biocidal composition for the treatment of water comprises a cationic polyquaternary ammonium biocide, together with a source of transition metal cations e.g. copper II cations and/or a biocide of the type containing a gem. bromonitromethylene group e.g. 2-bromo-2-nitropropane-1,3-diol.
Description
This is a continuation of application Ser. No. 07/180,368 filed on Apr. 11, 1988, now abandoned.
This invention relates to biocidal compositions for the treatment of water, and to methods for preventing microbial growth in water.
When water is used or retained in an open environment where it is subject to contamination by microorganisms, maintaining a suitable degree of sterility can be a problem. For example, recirculating water in cooling towers tends to become fouled by algal growths and bacterial slimes. Swimming pools become contaminated with algae and then by potentially dangerous bacteria. Similarly, industrial and agricultural lagoons. Process water from various industrial applications such as paper milling, and other recycled water, need to be treated to control microbiological growths.
Various agents have been proposed, and are commonly used, for the control of algae. The most frequently used today are oxidative substances such as hydrogen peroxide, sodium hypo-chlorite, and quaternary ammonium compounds such as n-alkyl dimethylbenzylammonium chlorides and n-alkyl dimethyl ethylbenzylammonium chlorides and analogous compounds. These substances are used to prevent microbial growth: that is to say they are added to water which has already been cleaned and sterilized (e.g. by filtration and chlorination), in order to maintain sterility. They are effective, typically at levels in the water of 10-100 ppm, although they do not necessarily provide a particularly wide spectrum of antimicrobial activity.
It is also well known that cations of transition metals such as copper and cobalt have algaecidal properties. Copper is particularly noted in this respect but has little, if any, activity against bacteria. One problem with the use of copper salts is that they tend to break down under neutral or slightly basic conditions to yield a precipitate of hydrated copper II hydroxide.
We have now discovered that a combination of transition metal cations, especially copper II cations, with a cationic polyquaternary ammonium biocidal compound or a quaternary ammonium biocide comprising one long chain alkyl group and three other groups selected from lower alkyl and aralkyl groups, has advantageous properties.
In particular, the combination of the quaternary compound and the metal ions in a concentrated aqueous system provides a stabilized metal ion solution which does not precipitate on dilution in the water to be treated. It may be theorized that the combination comprises some form of complex, since characteristic colour changes occur, e.g. the formation of an intense deep blue colour in dilute aqueous solutions of the copper II complex. The result is a distinct stabilization of the metal ions.
Thus, if copper sulphate (the blue pentahydrate) is dissolved in a concentrated aqueous solution of the quaternary ammonium compound, a clear common solution is formed. This solution can be added to the water, typically to give a quaternary compound level of 40 ppm and a copper level of 2.4 ppm without any precipitation of copper hydroxides or salts on dilution.
The quaternary compounds of choice are poly[hydroxyethylene(dimethylimino)β'-hydroxypropyl dimethylimino)methylene-dichloride], hereinafter referred to as PHE, such as the product sold by ABM Chemicals Limited of Woodley. Stockport, Cheshire SK6 1PQ ; poly[2-hydroxyethylene(dimethylimino)ethylene(dimethylimino) methylene dichloride]; and poly[hydroxyethylene(dimerhylimino)ethylene(dimethylimino)ethylene dichloride]. Other polymeric quaternary compounds comprise those carrying quaternised nitrogen atoms on side chains. Polyquaternary compounds are much preferred, giving good solubility and long lasting stability on dilution. Quaternary compounds such as didecyldimethyl ammonium chloride are unsatisfactory and tend to form insoluble complexes. Single quaternary compounds can be used, however, if the nitrogen atom is substituted by only one long chain alkyl group (e.g. C12 -C18), the remaining three substituents being lower alkyl, e.g. methyl, groups or aralkyl groups, e.g. benzyl or ethylbenzyl groups.
Typically, the transition metal ion content in the mixture should be sufficient to give a level of about 0.5 to 3 ppm in the treated water when the quaternary compound is present in the water at about 30 to 50 ppm. The metal is advantageously copper, but may for example be zinc, chromium or tin.
The concentrated mixture for addition to water can contain up to 50 or 60% of the quaternary compound and an equivalent amount of copper or other transition metal ions.
We provide, therefore, a biocidal composition containing a polymeric quaternary biocide, together with transition metal cations, especially copper II cations, and also a method of controlling microorganisms in water using such a composition.
In a separate feature of the invention, we have found that the quaternary biocides can also be enhanced in their bactericidal activity by formulation with a biocide of the type comprising a carbon atom substituted by a halogen atom and a nitro group, e.g. cyclic ##STR1## compounds and also 2-bromo-2-nitropropane-1,3-diol, supplied under the brand names Myacide by Boots Pure Drug Co., Nottingham and Bronopol by Henkel & Cie and 5-bromo-5-nitro-1,3-dioxane supplied under the brand name Bronidox by Henkel & Cie. These biocides have activity against a wider range of bacteria than quaternaries, and especially are active against pseudomonads. Myacide is usually used at a level of about 50-100 ppm.
Surprisingly we have now found that if Myacide or the like is formulated with a quaternary such as Glokill PQ so that at a dilution in water of the quaternary of about 20-30 ppm, the Myacide etc is present at about 0.5 to 5 ppm, the formulation is active against pseudomonads as well, even though the Myacide is present at levels far below those normally considered necessary. The two substances are mutually compatible, forming a stable co-solution concentrate and provide a powerful biocidal action on all water environments, especially pools and cooling towers. We therefore provide as a further feature of the invention biocidal compositions containing a halonitro biocide, and a quaternary biocide a ratio of from 1:50 to 1:10 by weight, and also a method of controlling microorganisms in water, using such a composition.
Three samples were compared:
Sample 1:
______________________________________
% by weight
______________________________________
PHE 83.0
2-bromo-2-nitro-propan-1,
2.5
3-diol (BNP)
CuSO.sub.4 7.0
4N HCl 0.5
Mains water 7.0
______________________________________
Sample 2: As Sample 1, but omitting the BNP
Sample 3: As Sample 1, but omitting the copper salt
Sample 4 As Sample 1, but replacing the BNP by 5-bromo-5-nitro-1,3-dioxan.
1. Culture Preparation
A 24 hour Tryptone Soya Agar (TSA) sloped culture of Pseudomonas aeruginosa NCTC 6750 was washed off using sterile distilled water (SDW) and diluted in SDW to approx. 108 organisms per ml.
2. Kill Tests
A range of dilutions of the test solutions were prepared in sterile standard World Health Organisation (WHO) Hard Water (see Appendix 1). At zero time P. aeruginosa inoculum was added to each dilution of each test solution to give approx. 106 organisms per ml. A control of sterile standard WHO hard water was also included. The tests were stored at 22° C. and sampled at 0 hours (control only), 24 hours, 48 hours and 72 hours. The number of viable bacteria was estimated using a pour plate technique (0.1% peptone water as diluent and TSA as growth medium). The pour plates were incubated at 30° C. for 3 days, surviving colonies counted and the dilution giving a 99.99% reduction in the bacterial population for each contact time calculated. The test was carried out on two separate occasions.
The number of surviving organisms for each test sample at each dilution and sampling time are shown in Tables 1 to 8
TABLE 1
______________________________________
Sample 1
Number of organisms per ml surviving in
ppm Time in hours
Dilution
Product 0 24 48 72
______________________________________
Control 0 4.5 × 10.sup.6
5.9 × 10.sup.6
3.0 × 10.sup.6
1.9 × 10.sup.6
1:5,000,000
0.2 -- 4.6 × 10.sup.6
5.6 × 10.sup.6
5.7 × 10.sup.6
1:2,000,000
0.5 -- 4.7 × 10.sup.6
6.9 × 10.sup.6
9.8 × 10.sup.6
1:1,000,000
1.0 -- 6.8 × 10.sup.3
2.6 × 10.sup.6
1.8 × 10.sup.6
1:500,000
2.0 -- 3.4 × 10.sup.3
7.9 × 10.sup.3
1.9 × 10.sup.5
1:200,000
5.0 -- 2.2 × 10.sup.3
3.9 × 10.sup.4
1.2 × 10.sup.5
1:100,000
10.0 -- 2.0 × 10.sup.1
<10 1.4 × 10.sup.2
______________________________________
-- count not required.
TABLE 2
______________________________________
Sample 2
Number of organisms per ml surviving in
ppm Time in hours
Dilution
Product 0 24 48 72
______________________________________
Control 0 4.5 × 10.sup.6
5.9 × 10.sup.6
3.0 × 10.sup.6
1.9 × 10.sup.6
1:5,000,000
0.2 -- 3.7 × 10.sup.6
6.8 × 10.sup.6
8.5 × 10.sup.6
1:2,000,000
0.5 -- 3.7 × 10.sup.6
5.2 × 10.sup.6
5.9 × 10.sup.6
1:1,000,000
1.0 -- 3.0 × 10.sup.4
7.6 × 10.sup.6
5.1 × 10.sup.6
1:500,000
2.0 -- 2.2 × 10.sup.2
3.2 × 10.sup.2
8.2 × 10.sup.4
1:200,000
5.0 -- 2.0 × 10.sup.2
4.1 × 10.sup.4
1.6 × 10.sup.5
1:100,000
10.0 -- 1.0 × 10.sup.1
<10 <10
______________________________________
-- count not required.
TABLE 3
______________________________________
Sample 3
Number of organisms per ml surviving in
ppm Time in hours
Dilution
Product 0 24 48 72
______________________________________
Control 0 4.5 × 10.sup.6
5.9 × 10.sup.6
3.0 × 10.sup.6
1.9 × 10.sup.6
1:5,000,000
0.2 -- 3.4 × 10.sup.6
3.9 × 10.sup.6
5.3 × 10.sup.6
1:2,000,000
0.5 -- 2.9 × 10.sup.6
3.7 × 10.sup.6
5.6 × 10.sup.6
1:1,000,000
1.0 -- 4.4 × 10.sup.5
4.7 × 10.sup.6
5.8 × 10.sup.6
1:500,000
2.0 -- 7.3 × 10.sup.4
2.2 × 10.sup.4
4.0 × 10.sup.4
1:200,000
5.0 -- 3.9 × 10.sup.2
1.9 × 10.sup.2
4.3 × 10.sup.3
1:100,000
10.0 -- 1.0 × 10.sup.1
<10 1.3 × 10.sup.2
______________________________________
-- count not required.
TABLE 4
______________________________________
Sample 4
Number of organisms per ml surviving in
ppm Time in hours
Dilution
Product 0 24 48 72
______________________________________
Control 0 4.5 × 10.sup.6
5.9 × 10.sup.6
3.0 × 10.sup.6
1.9 × 10.sup.6
1:5,000,000
0.2 -- 4.3 × 10.sup.6
5.9 × 10.sup.6
6.0 × 10.sup.6
1:2,000,000
0.5 -- 1.8 × 10.sup.6
4.7 × 10.sup.6
4.3 × 10.sup.6
1:1,000,000
1.0 -- 4.3 × 10.sup.4
5.2 × 10.sup.6
9.6 × 10.sup.6
1:500,000
2.0 -- 8.0 × 10.sup.4
9.3 × 10.sup.4
5.9 × 10.sup.5
1:200,000
5.0 -- 3.5 × 10.sup.3
2.5 × 10.sup.5
3.4 × 10.sup.4
1:100,000
10.0 -- 3.0 × 10.sup.1
9.6 × 10.sup.2
5.3 × 10.sup.4
______________________________________
-- count not required.
TABLE 5
______________________________________
TEST 2
Sample 1
Number of organisms per ml surviving in
ppm Time in hours
Dilution
Product 0 24 48 72
______________________________________
Control 0 2.8 × 10.sup.6
1.0 × 10.sup.6
1.4 × 10.sup.6
1.1 × 10.sup.7
1:1,000,000
1.0 -- 2.8 × 10.sup.5
8.4 × 10.sup.6
1.4 × 10.sup.7
1:500,000
2.0 -- 3.9 × 10.sup.3
5.6 × 10.sup.3
2.4 × 10.sup.5
1:200,000
5.0 -- 1.2 × 10.sup.3
8.0 × 10.sup.2
1.6 × 10.sup.3
1:100,000
10.0 -- 2.7 × 10.sup.3
3.8 × 10.sup.2
1.7 × 10.sup.2
1:50,000
20.0 -- 3.0 × 10.sup.1
1.0 × 10.sup.1
<10
1:20,000
50.0 -- 9.0 × 10.sup.2
<10 <10
1:10,000
100.0 -- 5.0 × 10.sup.2
2.0 × 10.sup.1
<10
______________________________________
-- count not required.
TABLE 6
______________________________________
Sample 2
Number of organisms per ml surviving in
ppm Time in hours
Dilution
Product 0 24 48 72
______________________________________
Control 0 2.8 × 10.sup.6
1.0 × 10.sup.6
1.4 × 10.sup.6
1.1 × 10.sup.7
1:1,000,000
1.0 -- 1.9 × 10.sup.6
1.4 × 10.sup.7
8.4 × 10.sup.6
1:500,000
2.0 -- 2.7 × 10.sup.3
9.0 × 10.sup.3
3.4 × 10.sup.5
1:200,000
5.0 -- 1.4 × 10.sup.3
3.7 × 10.sup.3
2.8 × 10.sup.5
1:100,000
10.0 -- 1.3 × 10.sup.3
1.8 × 10.sup.3
1.5 × 10.sup.4
1:50,000
20.0 -- <10 1.0 × 10.sup.1
1.0 × 10.sup.2
1:20,000
50.0 -- 2.5 × 10.sup.3
<10 1.6 × 10.sup.2
1:10,000
100.0 -- 1.0 × 10.sup.1
<10 <10
______________________________________
-- count not required.
TABLE 7
______________________________________
Sample 3
Number of organisms per ml surviving in
ppm Time in hours
Dilution
Product 0 24 48 72
______________________________________
Control 0 2.8 × 10.sup.6
1.0 × 10.sup.6
1.4 × 10.sup.6
1.1 × 10.sup.7
1:1,000,000
1.0 -- 2.6 × 10.sup.6
9.2 × 10.sup.6
8.4 × 10.sup.6
1:500,000
2.0 -- 6.0 × 10.sup.4
3.0 × 10.sup.5
2.3 × 10.sup.5
1:200,000
5.0 -- 1.3 × 10.sup.3
2.4 × 10.sup.3
1.5 × 10.sup.4
1:100,000
10.0 -- 1.8 × 10.sup.3
6.0 × 10.sup.2
1.5 × 10.sup.3
1:50,000
20.0 -- 1.2 × 10.sup.3
2.0 × 10.sup.1
<10
1:20,000
50.0 -- 6.0 × 10.sup.2
3.0 × 10.sup.1
<10
1:10,000
100.0 -- 3.0 × 10.sup.1
<10 <10
______________________________________
-- count not required.
TABLE 8
______________________________________
Sample 4
Number of organisms per ml surviving in
ppm Time in hours
Dilution
Product 0 24 48 72
______________________________________
Control 0 2.8 × 10.sup.6
1.0 × 10.sup.6
1.4 × 10.sup.6
1.1 × 10.sup.7
1:1,000,000
1.0 -- 3.4 × 10.sup.6
1.4 × 10.sup.7
8.0 × 10.sup.6
1:500,000
2.0 -- 1.9 × 10.sup.3
4.0 × 10.sup.3
6.0 × 10.sup.5
1:200,000
5.0 -- 2.0 × 10.sup.1
9.0 × 10.sup.1
9.0 × 10.sup.2
1:100,000
10.0 -- 1.0 × 10.sup.1
2.0 × 10.sup.1
2.3 × 10.sup.4
1:50,000
20.0 -- <10 <10 <10
1:20,000
50.0 -- <10 <10 <10
1:10,000
100.0 -- <10 <10 <10
______________________________________
-- count not required.
Linear regression was used to plot graphs of the log of number of colony forming units per ml. versus ppm of product. From these graphs the concentration of each product required, at each sampling time, to give 99.99% reduction in the bacterial population was determined. The values thus obtained for Test 1 and Test 2, and the corresponding dilution factors, are depicted in Tables 9 and 10.
TABLE 9
______________________________________
TEST 1
Contact Product required to give 99.99%
time in reduction in bacterial numbers
Product hours ppm dilution
______________________________________
Sample 1 24 6.3 1:158,730
48 7.6 1:132,450
72 10.1 1:99,009
Sample 2 24 5.5 1:183,486
48 6.6 1:151,515
72 7.4 1:134,589
Sample 3 24 6.3 1:159,235
48 approx 12.0 1:83,333
72 approx 15.5 1:64,516
Sample 4 24 6.1 1:163,934
48 5.9 1:169,491
72 9.0 1:111,111
______________________________________
TABLE 10
______________________________________
TEST 2
Contact Product required to give 99.99%
time in reduction in bacterial numbers
Product hours ppm dilution
______________________________________
Sample 1 24 105.2 1:9,505
48 44.5 1:22,471
72 24.0 1:41,666
Sample 2 24 60.5 1:16,528
48 40.5 1:24,691
72 37.5 1:26,666
Sample 3 24 74.5 1:13,422
48 46.0 1:21,739
72 28.0 1:35,714
Sample 4 24 28.5 1:35,087
48 31.5 1:31,746
72 28.5 1:35,087
______________________________________
Solution a
9.88 g MgCl2 ·6H2 O in 100 ml distilled water.
Filter sterilise.
Solution b
21.6 g CaCl2 (anhydrous) in 100 ml distilled water.
Filter sterilise.
Add 3 ml of solution a, plus 3 ml of solution b to 2 liters of sterile distilled water.
______________________________________
Zinc Replacing Copper II
Component % w/w
______________________________________
PHE 83
BNP 2.5
Zn SO.sub.4.7H.sub.2 O
7.0
4N HCl 0.5
Mains water 7.0
______________________________________
______________________________________ PHE 83% w/w BNP 2.5% w/w SnCl.sub.4 (ANHYD) 7.0% w/w 4N HCl 0.5% w/w Mains water 7.0% 2/w ______________________________________
______________________________________
When made
______________________________________
PHE 83% w/w
BNP 2.5% w/w
Sn.sub.2 Cl.sub.2.2H.sub.2 O
7.0% w/w
4N.HCl 0.5% w/w
Tap water 7.0% w.w
______________________________________
This product was cloudy when made, but on HEATING turned yellow and began to clear. There may have been some evaporation of the water.
______________________________________
Component Parts Final %
______________________________________
*WSCP 664 83
Myacide 20 2.5
CuSO.sub.4 5H.sub.2 O
56 7.0
**4NHCl 12 1.5
***Water 48 6.0
______________________________________
*WSCP claimed to be 60% solids (from Buckman, UK)
**Extra HCl added to lower pH to blue crystal 5.5
***Reduced H.sub.2 O to compensate for increased HCl
Note: Product does not go deep blue on dilution. EDTA/DTPA needed to give
colouration which is then deeper than with PHE.
1. Algistatic Trials
Minimum inhibitory concentrations (m.i.c.) were obtained against Chlorella emersonii.
______________________________________
m.i.c.
Sample (ppm)
______________________________________
Sample 1 10
Sample 3 10
Sample 2 10
Product of Example 2
15
______________________________________
2. Bactericidal Trials
______________________________________
a) Test Conditions
Biocide dilutions:
prepared in hard water (342
ppm hardness)
Test organism: Pseudomonas aeruginosa NCTC
6750
Temperature: 22° C.
Contact times: 24, 48 & 72 hours
Inactivator: 3% Tween 80 + 2% Soya
Lecithin
Result: concentration giving a mean
kill of 99.99%.
______________________________________
b) Results
Bactericidal Figure (ppm)
Sample 24 hrs 48 hrs 72 hrs
______________________________________
Sample 1 30 20 20
Sample 3 30 20 20
Sample 2 30 20 20
Product of Example 6
30 20 20
______________________________________
The following conclusions may be drawn.
1. Laboratory test suggest that the PHE/BNP/Cu blend will effectively control algal growth.
2. The PHE/BNP/Cu blend is a very effective bactericidal agent.
3. WSCP and PHE are readily interchangeable so far as the bactericidal performance is concerned.
(A) Three formulations were studied:
______________________________________
Formulation
Raw Material A B C
______________________________________
PHE 50 50 50
BNP 1 2 3
Citric Acid Monohydrate
0.5 0.5 0.5
Water 100 100 100
______________________________________
All formulations were tested for bactericidal activity in the presence of hard water (200 ppm hardness) with a 4 day contact time. Bacteria isolated from a very heavily contaminated swimming pool, which was proving extremely difficult to control, were used as the inoculum. The formulations were tested at concentrations of 100 and 150 ppm. It provided desirable to add the citric acid in order to ensure stability. Two trials were carried out.
(B) Eight different formulations and a control were used:
______________________________________
Sample 2
Formulation.sup.a
50% PHE from Ex. 1
BNP
______________________________________
(1) (Control)
0 0 0
(2) 50 0 0
(3) 50 50 0
(4) 100 50 0
(5) 0 0 2.5
(6) 0 0 5
(7) 50 0 2.5
(8) 50 50 2.5
(9) 100 50 5
______________________________________
.sup.a All values given in ppm.
Each formulation was made up in standard tap water (STW) and 20 ml. amounts of each were challenged with about 106 /ml P. aeruginosa NCTC 6750. Total viable counts (TVC's) were carried out in B.P. diluent and plated onto TSA at 0, 1, 2, 4 and 24 hours. Tests were stored at room temperature.
______________________________________
(A)
Concn.
Formulation
(ppm) Trial 1 Trial 2
______________________________________
A 150 +++ +++
100 ++++ ++++
B 150 + +
100 + ++
C 150 + -
100 + +
______________________________________
Key:
-: no growth of bacteria
+: slight growth
++: moderate growth
+++: heavy growth
++++: very heavy growth
(B)
Bacterial Count (numbers/ml) in Treated Water Samples
Formu- Time (hours)
lation 0 1 2 4 24
______________________________________
(1) 2.8 × 10.sup.6
2.6 × 10.sup.6
2.1 × 10.sup.6
2.8 × 10.sup.6
4.9 × 10.sup.5
(2) -- 8.0 × 10.sup.1
<10 <10 <10
(3) -- 1.1 × 10.sup.3
1.0 × 10.sup.2
<10 <10
(4) -- 1.4 × 10.sup.3
6.0 × 10.sup.1
<10 <10
(5) -- 2.2 × 10.sup.6
1.4 × 10.sup.6
1.2 × 10.sup.6
2.9 × 10.sup.5
(6) -- 2.2 × 10.sup.6
1.2 × 10.sup.6
1.4 × 10.sup.6
3.3 × 10.sup.5
(7) -- 9.0 × 10.sup.1
<10 <10 <10
(8) -- 2.3 × 10.sup.1
1.0 × 10.sup.1
<10 <10
(9) -- 5.4 × 10.sup.2
1.0 × 10.sup.1
<10 <10
______________________________________
Claims (10)
1. A biocide composition effective against Pseudomonas aeruginosa in water comprising
(a) a biocidally effective amount of a first biocide which is a quaternary ammonium biocide selected from the group consisting of poly[hydroxyethylene(dimethylimino)α'-hydroxypropyl(dimethylimino)methylene dichloride], poly[hydroxyethylene(dimethylimino)ethylene(dimethylimino)methylene dichloride] and poly[hydroxyethylene(dimethylimino)ethylene(dimethylimino)ethylene dichloride];
(b) a biocidally enhancing amount of a second biocide which is 2-bromo-2-nitropropane-1,3-diol; and
(c) an algicidally effective amount of a cation of copper,
wherein the weight ratio of the first biocide to the second biocide is 4:1 to 17:1.
2. The composition of claim 1, wherein the metal is copper.
3. A method of controlling Psudomonas aeruginosa microorganisms in water which comprises the application to the water of a biocide composition according to claim 1 in an amount such that the copper is present in the water in an amount of about 0.5 to 3 ppm.
4. A biocidal composition for the treatment of water comprising 10 parts of poly, an algicidally effective amount of copper sulfate, and one part of 2-bromo-2-nitropropane-1,3-diol.
5. A method of controlling Psudomonas aeruginosa microorganisms in water which comprises the application to the water of a biocide composition according to claim 4 in an amount such that the copper is present in the water in an amount of about 0.5 to 3 ppm.
6. The composition of claim 1, wherein the cationic polyquaternary ammonium biocide is poly[hydroxyethylene(dimethylimino)α'-hydroxypropyl(dimethylimino)methylene-dichloride].
7. The composition of claim 6, containing the copper in the form of copper sulfate.
8. A method of controlling Psudomonas aeruginosa microorganisms in water which comprises the application to the water of a biocide composition according to claim 6 in an amount such that the copper is present in the water in an amount of about 0.5 to 3 ppm.
9. A method of controlling Psudomonas aeruginosa microorganisms in water which comprises the application to the water of a biocide composition according to claim 7 in an amount such that the copper is present in the water in an amount of about 0.5 to 3 ppm.
10. The composition of claim 7 which contains about 0.5 to 3 parts of copper for about 30 to 50 parts of the first biocide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/673,851 US5171350A (en) | 1987-04-09 | 1991-03-21 | Biocide |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8708501 | 1987-04-09 | ||
| GB878708501A GB8708501D0 (en) | 1987-04-09 | 1987-04-09 | Biocide |
| US18036888A | 1988-04-11 | 1988-04-11 | |
| US07/673,851 US5171350A (en) | 1987-04-09 | 1991-03-21 | Biocide |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US18036888A Continuation | 1987-04-09 | 1988-04-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5171350A true US5171350A (en) | 1992-12-15 |
Family
ID=27263376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/673,851 Expired - Fee Related US5171350A (en) | 1987-04-09 | 1991-03-21 | Biocide |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US5171350A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387415B1 (en) * | 1995-06-07 | 2002-05-14 | Bio-Lab, Inc. | Sequestered metal biocides using ionic polymeric stabilizing agents |
| JP3424010B2 (en) | 1994-12-14 | 2003-07-07 | 株式会社片山化学工業研究所 | Algae controlling agent and algal controlling method II |
| US20070212425A1 (en) * | 2006-03-09 | 2007-09-13 | Barna Ivan J | Cidal formulations and methods of use |
| EP1541715B1 (en) * | 2003-12-09 | 2012-03-28 | General Electric Company | Method of inhibiting corrosion in a steam condensate system |
| US8522585B1 (en) | 2006-05-23 | 2013-09-03 | Pmx Industries Inc. | Methods of maintaining and using a high concentration of dissolved copper on the surface of a useful article |
| US9796914B2 (en) | 2013-05-07 | 2017-10-24 | Baker Hughes Incorporated | Hydraulic fracturing composition, method for making and use of same |
| US9809742B2 (en) | 2013-05-07 | 2017-11-07 | Baker Hughes, A Ge Company, Llc | Hydraulic fracturing composition, method for making and use of same |
| US9828844B2 (en) | 2013-05-07 | 2017-11-28 | BAKER HUGHTES, a GE company, LLC | Hydraulic fracturing composition, method for making and use of same |
| US10563042B2 (en) | 2016-12-14 | 2020-02-18 | Ecolab Usa Inc. | Quaternary cationic polymers |
| US11427964B2 (en) | 2018-06-12 | 2022-08-30 | Ecolab Usa Inc. | Quaternary cationic surfactants and polymers for use as release and coating modifying agents in creping and tissue papers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0059978B1 (en) * | 1981-03-10 | 1984-06-13 | BAYROL Chemische Fabrik G.m.b.H. | Process for the chemical treatment and disinfection of waters and aqueous systems |
| US4499077A (en) * | 1981-02-03 | 1985-02-12 | Stockel Richard F | Anti-microbial compositions and associated methods for preparing the same and for the disinfecting of various objects |
| US4719083A (en) * | 1985-04-29 | 1988-01-12 | Chemed Corporation | Composition useful as corrosion inhibitor, anti-scalant and continuous biocide for water cooling towers and method of use |
-
1991
- 1991-03-21 US US07/673,851 patent/US5171350A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4499077A (en) * | 1981-02-03 | 1985-02-12 | Stockel Richard F | Anti-microbial compositions and associated methods for preparing the same and for the disinfecting of various objects |
| EP0059978B1 (en) * | 1981-03-10 | 1984-06-13 | BAYROL Chemische Fabrik G.m.b.H. | Process for the chemical treatment and disinfection of waters and aqueous systems |
| US4719083A (en) * | 1985-04-29 | 1988-01-12 | Chemed Corporation | Composition useful as corrosion inhibitor, anti-scalant and continuous biocide for water cooling towers and method of use |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3424010B2 (en) | 1994-12-14 | 2003-07-07 | 株式会社片山化学工業研究所 | Algae controlling agent and algal controlling method II |
| US6387415B1 (en) * | 1995-06-07 | 2002-05-14 | Bio-Lab, Inc. | Sequestered metal biocides using ionic polymeric stabilizing agents |
| EP1541715B1 (en) * | 2003-12-09 | 2012-03-28 | General Electric Company | Method of inhibiting corrosion in a steam condensate system |
| US20070212425A1 (en) * | 2006-03-09 | 2007-09-13 | Barna Ivan J | Cidal formulations and methods of use |
| US8522585B1 (en) | 2006-05-23 | 2013-09-03 | Pmx Industries Inc. | Methods of maintaining and using a high concentration of dissolved copper on the surface of a useful article |
| EP2886676A2 (en) | 2006-05-23 | 2015-06-24 | PMX Industries, Inc. | Product having a specific surface roughness and a high concentration of dissolved copper on its surface |
| US9796914B2 (en) | 2013-05-07 | 2017-10-24 | Baker Hughes Incorporated | Hydraulic fracturing composition, method for making and use of same |
| US9809742B2 (en) | 2013-05-07 | 2017-11-07 | Baker Hughes, A Ge Company, Llc | Hydraulic fracturing composition, method for making and use of same |
| US9828844B2 (en) | 2013-05-07 | 2017-11-28 | BAKER HUGHTES, a GE company, LLC | Hydraulic fracturing composition, method for making and use of same |
| US10138418B2 (en) | 2013-05-07 | 2018-11-27 | Baker Hughes, A Ge Company, Llc | Hydraulic fracturing composition, method for making and use of same |
| US10563042B2 (en) | 2016-12-14 | 2020-02-18 | Ecolab Usa Inc. | Quaternary cationic polymers |
| US11319427B2 (en) | 2016-12-14 | 2022-05-03 | Ecolab Usa Inc. | Quaternary cationic polymers |
| US11427964B2 (en) | 2018-06-12 | 2022-08-30 | Ecolab Usa Inc. | Quaternary cationic surfactants and polymers for use as release and coating modifying agents in creping and tissue papers |
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